Metal‐Ligand Bonds Based Reprogrammable and Re‐Processable Supramolecular Liquid Crystal Elastomer Network

Dynamic covalent bonds endow liquid crystal elastomers (LCEs) with network rearrangeability, facilitating the fixation of mesogen alignment induced by external forces and enabling reversible actuation. In comparison, the bond exchange of supramolecular interactions is typically too significant to stably maintain the programmed alignment, particularly under intensified external stimuli. Nevertheless, remaking and recycling of supramolecular interaction‐based polymer networks are more accessible than those based on dynamic covalent bonds, as the latter are difficult to completely dissociate. Thus, preparing an LCE that possesses both supramolecular‐like exchangeability and covalent bond‐level stability remains a significant challenge. In this work, we addressed this issue by employing metal‐ligand bonds as the crosslinking points of LCE networks. As such, mesogen alignment can be repeatedly encoded through metal‐ligand bond exchange and stably maintained after programming, since the bond exchange rate is sufficiently slow when the programming and actuation temperatures are below the bond dissociation temperature. More importantly, the metal‐ligand bonds can be completely dissociated at high temperatures, allowing the LCE network to be dissolved in a solvent and reshaped into desired geometries via solution casting. Building on these properties, our LCEs can be fabricated into versatile actuators, such as reversible folding origami, artificial muscles, and soft robotics. A dynamic crosslinked LCE network based on metal‐ligand bonds can achieve orientation programming of liquid crystal mesogen via partial stress relaxation. This programmed LCE maintains stable actuation even at elevated temperatures due to the high strength of metal‐ligand bonds comparable to traditional covalent bonds. The flexible and reversible nature of metal‐ligand interactions also allows for the reprogramming of actuation behaviors and enables reprocessing and reshaping upon complete dissociation.